A wholly aromatic thermotropic liquid crystalline polymer and compositions including the liquid crystalline polymer are described. The polymer composition can include the liquid crystalline polymer and a fibrous filler, e.g., a chopped glass or milled glass fibrous filler. The compositions are capable of exhibiting excellent mechanical properties. The liquid crystalline polymer provides desirable characteristics with the incorporation of little or no naphthenic acids in the polymer backbone.
|
1. A thermotropic liquid crystalline polymer composition that comprises a melt-polymerized, wholly aromatic liquid crystalline polymer and a fibrous filler, wherein the total amount of repeating units in the liquid crystalline polymer derived from naphthenic acids is no more than about 5 mol. %, wherein the liquid crystalline polymer comprises repeating units derived from isophthalic acid, hydroquinone, and at least one hydroxycarboxylic acid and wherein the polymer composition has a flexural modulus of greater than about 10,000 megaPascals as determined in accordance with ISO Test No. 178 at 23° C. #5#
2. The thermotropic liquid crystalline polymer composition of 3. The thermotropic liquid crystalline polymer composition of 4. The thermotropic liquid crystalline polymer composition of 5. The thermotropic liquid crystalline polymer composition of 6. The thermotropic liquid crystalline polymer composition of 7. The thermotropic liquid crystalline polymer composition of 8. The thermotropic liquid crystalline polymer composition of 9. The thermotropic liquid crystalline polymer composition of 10. The thermotropic liquid crystalline polymer composition of 11. The thermotropic liquid crystalline polymer composition of 12. The thermotropic liquid crystalline polymer composition of 13. The thermotropic liquid crystalline polymer composition of 14. The thermotropic liquid crystalline polymer composition of 15. The thermotropic liquid crystalline polymer composition of 16. The thermotropic liquid crystalline polymer composition of 17. The thermotropic liquid crystalline polymer composition of 18. The thermotropic liquid crystalline polymer composition of 19. The thermotropic liquid crystalline polymer composition of 20. The thermotropic liquid crystalline polymer composition of 21. The thermotropic liquid crystalline polymer composition of
22. The thermotropic liquid crystalline polymer composition of |
Thermotropic liquid crystalline polymers are wholly aromatic condensation polymers that have relatively rigid and linear polymer chains. When these polymers melt they orient to form a liquid crystal phase. The formulations are generally derived from aromatic hydroxy acid monomers (e.g., hydroxybenzoic acid (“HBA”) or 6-hydroxy-2-naphthenic acid (“HNA”)), either alone or in conjunction with other aromatic monomers, such as diacids (e.g., terephthalic acid (“TA”) or isophthalic acid (“IA”)) and/or dials (e.g., hydroquinone (“HQ”), acetaminophen (“APAP”), and 4,4′-biphenol (“BP”)). Liquid crystalline polymers make up a family of thermoplastics that have a unique set of properties. They perform very well in harsh environments, exhibiting high heat resistance and tolerance, high electrical resistance, and high chemical resistance. Although liquid crystalline polymers have many unique advantages, they also have shown disadvantages. For instance, the strength characteristics exhibited by liquid crystalline polymers are often not adequate for certain applications such as thin-walled portions of electrical connectors, printer parts, etc. Moreover, as the demand grows for small and light products, polymers that exhibit adequate mechanical characteristics are being sought as replacement for heavier metal materials, for instance as framing for portable electronics.
Efforts have been made to improve the physical characteristics of liquid crystalline polymers through various means including the formation of blends with other polymers, the introduction of certain fillers into the liquid crystalline polymer composition such as specific amounts of inorganic fillers, the inclusion of small molecules or oligomers into a blend, the incorporation of additional monomer units into the polymer backbone as a repeating unit, and so forth. One commonly employed method for improving physical characteristics of liquid crystalline polymers is through incorporation of a naphthenic acid chain disrupter into the polymer backbone. For instance, HNA has been incorporated into the polymer, and is generally believed to disrupt the linear nature of the polymer backbone and thereby affect characteristics of the polymer, such as melting temperature. Unfortunately, the utilization of naphthenic acid derivatives as a chain disrupter can lead to other less desirable results. For instance, reactivity of the naphthenic acids with other monomeric constituents can occur and may have unintended consequences on the final properties of the polymer composition. Moreover, high amounts of naphthenic chain disrupters can lead to a lower level of molecular orientation, which can affect mechanical properties. In addition to functional concerns, the high cost of naphthenic acids alone dictates that the need for avoidance of these materials.
As such, a need continues to exist for a thermotropic liquid crystalline polymer that exhibits desired mechanical characteristics while avoiding undesired issues as have been encountered in the past.
In accordance with one embodiment of the present invention, a thermotropic liquid crystalline polymer composition is disclosed that comprises a melt-polymerized, wholly aromatic liquid crystalline polymer and a fibrous filler. For instance, the total amount of repeating units in the liquid crystalline polymer derived from naphthenic acids can be no more than about 5 mol. %. In addition, the repeating units in the liquid crystalline polymer include units derived from isophthalic acid, from hydroquinone, and from at least one hydroxycarboxylic acid. In addition, the polymer composition can have a flexural modulus of greater than about 10,000 megaPascals as determined in accordance with ISO Test No. 178 at 23° C.
Other features and aspects of the present invention are set forth in greater detail below.
A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:
It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Generally speaking, the present invention is directed to a wholly aromatic thermotropic liquid crystalline polymer and compositions including the liquid crystalline polymer capable of exhibiting excellent mechanical properties. For instance, the polymer composition can include the liquid crystalline polymer and a fibrous filler. Beneficially, the liquid crystalline polymer provides desirable characteristics with the incorporation of little or no naphthenic acids in the polymer backbone. For instance, a composition incorporating the liquid crystalline polymer may exhibit excellent tensile modulus and flexural modulus characteristics, which may be considered a measure of the overall stiffness of the polymer composition. By way of example, a polymer composition can have a tensile modulus of greater than about 10,000 MPa, greater than about 16,000 MPa, greater than about 18,000 MPa, greater than about 20,000 MPa, or greater than about 22,000 MPa as determined according to ISO Test No. 527 (technically equivalent to ASTM D638) at a temperature of 23° C. The polymer composition can also have flexural strength of greater than about 16,000 MPa, greater than about 19,000 MPa, greater than about 21,000 MPa, or greater than about 23,000 MPa as determined according to ISO Test No. 178 (technically equivalent to ASTM D790) at a temperature of 23° C.
The ability to form a polymer with the properties noted above may be achieved by the use of isophthalic acid and hydroquinone on the polymer backbone in conjunction with the polymer having little or no naphthenic acid derivatives. More specifically, the liquid crystalline polymer can utilize isophthalic acid and hydroquinone in place of conventional naphthenic acid chain disrupters (e.g., HNA) utilized in the past. For instance, the isophthalic acid and hydroquinone can be utilized in a ratio to one another of from about 2:1 to about 1:2, from about 3:2 to about 2:3 or from about 4:5 to about 5:4. In one embodiment, the isophthalic acid and the hydroquinone can be utilized in a ratio to one another of about 1:1. Without wishing to be bound to any particular theory, it is believed that through utilization of a combination of isophthalic acid and hydroquinone rather than a naphthenic acid chain disruptor, the linearity of the polymer can be increased, which can improve the strength characteristics of the polymer.
The precursor monomers employed during the formation of the liquid crystalline polymer can include the isophthalic acid and the hydroquinone in addition to one or more additional precursor monomers. The additional precursor monomer employed may generally vary as is known in the art. For example, suitable thermotropic liquid crystalline polymers may be aromatic polyesters, aromatic poly(esteramides), aromatic poly(estercarbonates), aromatic polyamides, etc., and as such contain repeating units formed from one or more aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic dials, aromatic aminocarboxylic acids, aromatic amines, aromatic diamines, etc., as well as combinations thereof in conjunction with the isophthalic acid and the hydroquinone.
In general, the monomer units derived from hydroquinone may constitute from about 1 mol. % to about 25 mol. %, in some embodiments from about 2 mol. % to about 20 mol. %, and in some embodiments, from about 2 mol. % to about 18 mol. % of the polymer. The monomer units derived from isophthalic acid may constitute from about 1 mol. % to about 30 mol. %, in some embodiments from about 2 mol. % to about 25 mol. %, and in some embodiments, from about 2 mol. % to about 23 mol. % of the polymer. The remainder monomer units of the polymer can be derived from additional precursor monomers as are generally known in the art.
Aromatic polyesters, for instance, may be obtained by polymerizing hydroquinone and isophthalic acid in conjunction with at least one aromatic hydroxycarboxylic acid. The aromatic polyester may optionally include additional diols and/or dicarboxylic acids, as are known. Examples of suitable aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid; 4-hydroxy-4′-biphenylcarboxylic acid; 4′-hydroxyphenyl-4-benzoic acid; 3′-hydroxyphenyl-4-benzoic acid; 4′-hydroxyphenyl-3-benzoic acid, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof.
Examples of aromatic dicarboxylic acids include terephthalic acid; 2,6-naphthalenedicarboxylic acid; diphenyl ether-4,4′-dicarboxylic acid; 1,6-naphthalenedicarboxylic acid; 2,7-naphthalenedicarboxylic acid; 4,4′-dicarboxybiphenyl; bis(4-carboxyphenyl)ether; bis(4-carboxyphenyl)butane; bis(4-carboxyphenyl)ethane; bis(3-carboxyphenyl)ether; bis(3-carboxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof. Examples of aromatic diols include resorcinol; 4,4′-dihydroxybiphenyl; 3,3′-dihydroxybiphenyl; 3,4′-dihydroxybiphenyl; 4,4′-dihydroxybiphenyl ether; bis(4-hydroxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof.
Liquid crystalline polyesteramides may likewise be obtained by polymerizing the isophthalic acid and hydroquinone with at least one aromatic aminocarboxylic acid and/or at least one aromatic amine and/or diamine optionally having phenolic hydroxy groups. The liquid crystalline polyesteramide may also incorporate one or more additional aromatic hydroxycarboxylic acid and/or aromatic dicarboxylic acid as described above. Suitable aromatic amines and diamines may include, for instance, 3-aminophenol; 4-aminophenol; 1,4-phenylenediamine; 1,3-phenylenediamine, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof. For example, a liquid crystalline polyesteramide can be obtained by polymerizing isophthalic acid, hydroquinone, and N-acetyl-4-aminophenol (commonly termed APAP or acetaminophen) with a hydroxycarboxylic acid, optionally in conjunction with one or more additional monomeric constituents as described.
While not necessarily required in all embodiments, it is generally desired to minimize the content of repeating units derived from hydroxynaphthenic acids, such as 6-hydroxy-2-naphthenic acid (HNA). That is, the total amount of repeating units derived from hydroxynaphthenic acids is typically no more than about 5 mol. %, in some embodiments no more than about 3 mol. %, and in some embodiments, from 0 mol. % to about 2 mol. % (e.g., 0 mol. %) of the polymer. Likewise, of the precursor monomer(s) employed during melt polymerization, no more than about 5 mol. %, in some embodiments no more than about 3 mol. %, and in some embodiments, from 0 mol. % to about 2 mol. % (e.g., 0 mol. %) are hydroxynaphthenic acids. In one embodiment, the liquid crystalline polymer will not include any hydroxynaphthenic acid monomers in the backbone.
The liquid crystalline polymer can be formed with a minimum amount of repeating units derived from naphthenic dicarboxylic acids. For instance, the total amount of repeating units derived from naphthenic hydroxycarboxylic and/or dicarboxylic acids (e.g., NDA, HNA, or a combination of HNA and NDA) can be no more than about 5 mol. %, in some embodiments no more than about 3 mol. %, and in some embodiments, from 0 mol. % to about 2 mol. % (e.g., 0 mol. %) of the polymer. For instance, of the precursor monomer(s) employed during melt polymerization, there may be no naphthenic hydroxycarboxylic acids and no more than about 5 mol. %, in some embodiments no more than about 3 mol. %, and in some embodiments, from 0 mol. % to about 2 mol. % (e.g., 0 mol. %) may be naphthenic dicarboxylic acids.
Despite the absence of a high level of conventional naphthenic acids, it is believed that the resulting “low naphthenic” polymers are still capable of exhibiting good heat resistance at a lower melting temperature while exhibiting excellent mechanical characteristics. In one embodiment, a liquid crystalline esteramide is derived from isophthalic acid, hydroquinone, a hydroxycarboxylic acid and N-acetyl-4-aminophenol. Other monomeric units may optionally be employed such as other aromatic hydroxy carboxylic acids (e.g., terephthalic acid) and/or aromatic diols (e.g., 4,4′-biphenol, resorcinol, etc.). Terephthalic acid may, for example, constitute from about 1 mol. % to about 25 mol. %, in some embodiments from about 2 mol. % to about 20 mol. %, and in some embodiments, from about 5 mol. % to about 15 mol. % of the polymer. Resorcinol and/or 4,4′-biphenol may likewise constitute from about 1 mol. % to about 15 mol. %, when employed.
In one particular embodiment, a liquid crystalline esteramide is derived from isophthalic acid, hydroquinone, 4-hydroxybenzoic acid, terephthalic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-4-aminophenol. The monomer units derived from isophthalic acid may constitute from about 1% to about 5% of the polymer on a mole basis (e.g., 2%-3%), the monomer units derived from hydroquinone may constitute from about 1% to about 5% of the polymer on a mole basis (e.g., 2%-3%), the monomer units derived from 4-hydroxybenzoic acid may constitute from about 30% to about 90% of the polymer on a mole basis (e.g., 50%-70%), the monomer units derived from terephthalic acid may constitute from about 5% to about 50% (e.g., 20%) of the polymer on a mole basis, the monomer units derived from 4-4′-dihydroxybiphenyl may constitute from about 1% to about 20% of the polymer on a mole basis (e.g., 5%-15%), and the monomer units derived from N-acetyl-4-aminophenol may constitute from about 2% to about 15% (e.g., 5%-10%) of the polymer on a mole basis.
Regardless of their additional constituents, the liquid crystalline polymers may be prepared by introducing the appropriate monomer(s) (e.g., hydroquinone, isophthalic acid, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic dial, aromatic amine, aromatic diamine, etc.) into a reactor vessel to initiate a polycondensation reaction. The vessel employed for the reaction is not especially limited, although it is typically desired to employ one that is commonly used in reactions of high viscosity fluids. Examples of such a reaction vessel may include a stirring tank-type apparatus that has an agitator with a variably-shaped stirring blade, such as an anchor type, multistage type, spiral-ribbon type, screw shaft type, etc., or a modified shape thereof. Further examples of such a reaction vessel may include a mixing apparatus commonly used in resin kneading, such as a kneader, a roll mill, a Banbury mixer, etc.
If desired, the reaction may proceed through the acetylation of the monomers as referenced above and known the art. This may be accomplished by adding an acetylating agent (e.g., acetic anhydride) to the monomers. Acetylation is generally initiated at temperatures of about 90° C. During the initial stage of the acetylation, reflux may be employed to maintain vapor phase temperature below the point at which acetic acid byproduct and anhydride begin to distill. Temperatures during acetylation typically range from between 90° C. to 150° C., and in some embodiments, from about 110° C. to about 150° C. If reflux is used, the vapor phase temperature typically exceeds the boiling point of acetic acid, but remains low enough to retain residual acetic anhydride. For example, acetic anhydride vaporizes at temperatures of about 140° C. Thus, providing the reactor with a vapor phase reflux at a temperature of from about 110° C. to about 130° C. is particularly desirable. To ensure substantially complete reaction, an excess amount of acetic anhydride may be employed. The amount of excess anhydride will vary depending upon the particular acetylation conditions employed, including the presence or absence of reflux. The use of an excess of from about 1 to about 10 mole percent of acetic anhydride, based on the total moles of reactant hydroxyl groups present is not uncommon.
Acetylation may occur in a separate reactor vessel, or it may occur in situ within the polymerization reactor vessel. When separate reactor vessels are employed, one or more of the monomers may be introduced to the acetylation reactor and subsequently transferred to the polymerization reactor. Likewise, one or more of the monomers may also be directly introduced to the reactor vessel without undergoing pre-acetylation. In addition to the monomers and optional acetylating agents, other materials may also be included within the reaction mixture to help facilitate polymerization. For instance, a catalyst may be optionally employed, such as metal salt catalysts (e.g., magnesium acetate, tin(I) acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, etc.) and organic compound catalysts (e.g., N-methylimidazole). Such catalysts are typically used in amounts of from about 50 to about 500 parts per million based on the total weight of the recurring unit precursors. When separate reactors are employed, it is typically desired to apply the catalyst to the acetylation reactor rather than the polymerization reactor, although this is by no means a requirement.
The reaction mixture is generally heated to an elevated temperature within the polymerization reactor vessel to initiate melt polycondensation of the reactants. Polycondensation may occur, for instance, within a temperature range of from about 210° C. to about 400° C., and in some embodiments, from about 250° C. to about 350° C. For instance, one suitable technique for forming an aromatic polyester may include charging precursor monomers (e.g., hydroquinone and isophthalic acid in conjunction with one or more additional monomers) and acetic anhydride into the reactor, heating the mixture to a temperature of from about 90° C. to about 150° C. to acetylize a hydroxyl group of the monomers (e.g., forming acetoxy), and then increasing the temperature to a temperature of from about 210° C. to about 400° C. to carry out melt polycondensation. As the final polymerization temperatures are approached, volatile byproducts of the reaction (e.g., acetic acid) may also be removed so that the desired molecular weight may be readily achieved. The reaction mixture is generally subjected to agitation during polymerization to ensure good heat and mass transfer, and in turn, good material homogeneity. The rotational velocity of the agitator may vary during the course of the reaction, but typically ranges from about 10 to about 100 revolutions per minute (“rpm”), and in some embodiments, from about 20 to about 80 rpm. To build molecular weight in the melt, the polymerization reaction may also be conducted under vacuum, the application of which facilitates the removal of volatiles formed during the final stages of polycondensation. The vacuum may be created by the application of a suctional pressure, such as within the range of from about 5 to about 30 pounds per square inch (“psi”), and in some embodiments, from about 10 to about 20 psi.
Following melt polymerization; the molten polymer may be discharged from the reactor, typically through an extrusion orifice fitted with a die of desired configuration, cooled, and collected. Commonly, the melt is discharged through a perforated die to form strands that are taken up in a water bath, pelletized and dried. The resin may also be in the form of a strand, granule, or powder. While unnecessary, it should also be understood that a subsequent solid phase polymerization may be conducted to further increase molecular weight. When carrying out solid-phase polymerization on a polymer obtained by melt polymerization, it is typically desired to select a method in which the polymer obtained by melt polymerization is solidified and then pulverized to form a powdery or flake-like polymer, followed by performing solid polymerization method, such as a heat treatment in a temperature range of 200° C. to 350° C. under an inert atmosphere (e.g., nitrogen).
Regardless of the particular method employed, the resulting liquid crystalline polymer typically has a number average molecular weight (Mn) of about 2,000 grams per mole or more, in some embodiments from about 4,000 grams per mole or more, and in some embodiments, from about 5,000 to about 30,000 grams per mole, Of course, it is also possible to form polymers having a lower molecular weight, such as less than about 2,000 grams per mole, using the method of the present invention. The intrinsic viscosity of the polymer, which is generally proportional to molecular weight, may likewise be about 2 deciliters per gram (“dL/g”) or more, in some embodiments about 3 dL/g or more, in some embodiments from about 4 to about 20 dL/g, and in some embodiments from about 5 to about 15 dL/g. Intrinsic viscosity may be determined in accordance with ISO-1628-5 using a 50/50 (v/v) mixture of pentafluorophenol and hexafluoroisopropanol. According to this method, each sample is prepared in duplicate by weighing about 0.02 grams into a 22 mL vial. 10 mL of pentafluorophenol (“PFP”) is added to each vial and the solvent. The vials are placed in a heating block set to 80° C. overnight. The following day 10 mL of hexafluoroisopropanol (“HFIP”) is added to each vial. The final polymer concentration of each sample is generally about 0.1%. The samples are allowed to cool to room temperature and analyzed using viscometer, for instance a PolyVisc automatic viscometer.
In forming a polymer composition, the liquid crystalline polymer is combined with a fibrous filler. The fibrous filler may include one or more fiber types including, without limitation, polymer fibers, glass fibers, carbon fibers, metal fibers, natural fibers such as jute, bamboo, etc., basalt fibers, and so forth, or a combination of fiber types. The total amount of fibrous fillers may, for example, constitute from about 10 wt. % to about 90 wt. %, in some embodiments from about 20 wt. % to about 60 wt. %, and in some embodiments, from about 25 wt. % to about 55 wt. % of the composition.
The fibers used in the polymer composition generally have a high degree of tensile strength relative to their mass. For example, the ultimate tensile strength of the fibers (determined in accordance with ASTM D2101) is typically from about 1,000 to about 15,000 megaPascals (“MPa”), in some embodiments from about 2,000 MPa to about 10,000 MPa, and in some embodiments, from about 3,000 MPa to about 6,000 MPa. To help maintain an insulative property, which is often desirable when employed in electrical components, the high strength fibers may be formed from materials that are also generally insulative in nature, such as glass, ceramics (e.g., alumina or silica), aramids (e.g., Kevlar® marketed by E. I. duPont de Nemours, Wilmington, Del.), polyolefins, polyesters, etc., as well as mixtures thereof. Glass fibers are particularly suitable, such as E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, etc., and mixtures thereof.
The average length of the fibers in the polymer composition may vary. For instance, in one embodiment, chopped fibers, e.g., chopped glass fibers can be utilized having an initial length of from about 1 millimeter to about 20 millimeters, from about 2 millimeters to about 10 millimeters, or from about 3 millimeters to about 6 millimeters. The nominal diameter of the chopped glass fibers can generally be from about 2 micrometers to about 50 micrometers, for instance from about 5 micrometers to about 20 micrometers.
Milled glass fibers may be utilized as a fibrous filler for the polymer composition, either in combination with chopped fibers or alternative to chopped fibers. The milled fibers may, for example, have a length of from about 10 micrometers to about 200 micrometers or from about 20 micrometers to about 75 micrometers.
The nominal diameter of the fibers, including both chopped and milled fibers, can generally be from about 10 micrometers to about 35 micrometers, and in some embodiments, from about 15 micrometers to about 30 micrometers. In one embodiment, the fibers may have a relatively high aspect ratio (average length divided by nominal diameter). For example, the fibers may have an aspect ratio of from about 2 to about 50, in some embodiments from about 4 to about 40, and in some embodiments, from about 5 to about 20 are particularly beneficial.
The fibers may be pretreated with a sizing as is generally known. In one embodiment, the fibers may have a high yield or small K numbers. The tow is indicated by the yield or K number. For instance, glass fiber tows may have 50 yield and up, for instance from about 115 yield to about 1200 yield.
In addition to the fibers noted above, other additives that can be included in the composition may include, for instance, antimicrobials, fillers, pigments, antioxidants, stabilizers, surfactants, waxes, flow promoters, solid solvents, and other materials added to enhance properties and processability. For instance, mineral fillers may be employed in the polymer composition to help achieve a smooth surface appearance. When employed, such mineral fillers typically constitute from about 1 wt. % to about 40 wt. %, in some embodiments from about 2 wt. % to about 35 wt. %, and in some embodiments, from about 5 wt. % to about 30 wt. % of the polymer composition. Clay minerals may be particularly suitable for use in the present invention. Examples of such clay minerals include, for instance, talc (Mg3Si4O10(OH)2), halloysite (Al2Si2O5(OH)4), kaolinite (Al2Si2O5(OH)4), illite ((K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]), montmorillonite (Na,Ca)0.33(Al,Mg)2Si4O10(OH)2.nH2O), vermiculite ((MgFe,Al)3(Al,Si)4O10(OH)2.4H2O), palygorskite ((Mg,Al)2Si4O10(OH).4(H2O)), pyrophyllite (Al2Si4O10(OH)2), etc., as well as combinations thereof. In lieu of, or in addition to, clay minerals, still other mineral fillers may also be employed. For example, other suitable silicate fillers may also be employed, such as calcium silicate, aluminum silicate, aluminum hydroxide (alumina trihydrate (ATH)), mica, diatomaceous earth, wollastonite, and so forth. Mica, for instance, may be particularly suitable. There are several chemically distinct mica species with considerable variance in geologic occurrence, but all have essentially the same crystal structure. As used herein, the term “mica” is meant to generically include any of these species, such as muscovite (KAl2(AlSi3)O10(OH)2), biotite (K(Mg,Fe)3(AlSi3)O10(OH)2), phlogopite (KMg3(AlSi3)O10(OH)2), lepidolite (K(Li,Al)2-3(AlSi3)O10(OH)2), glauconite (K,Na)(Al,Mg,Fe)2(Si,Al)4O10(OH)2), etc., as well as combinations thereof.
Lubricants that are capable of withstanding the processing conditions of the liquid crystalline polymer without substantial decomposition may also be employed in the polymer composition. Examples of such lubricants include fatty acids esters, the salts thereof, esters, fatty acid amides, organic phosphate esters, and hydrocarbon waxes of the type commonly used as lubricants in the processing of engineering plastic materials, including mixtures thereof. Suitable fatty acids typically have a backbone carbon chain of from about 12 to about 60 carbon atoms, such as myristic acid, palmitic acid, stearic acid, arachic acid, montanic acid, octadecanoic acid, parinaric acid, and so forth. Suitable esters include fatty acid esters, fatty alcohol esters, wax esters, glycerol esters, glycol esters and complex esters, Fatty acid amides include fatty primary amides, fatty secondary amides, methylene and ethylene bisamides and alkanolamides such as, for example, palmitic acid amide, stearic acid amide, oleic acid amide, N,N′-ethylenebisstearamide and so forth. Also suitable are the metal salts of fatty adds such as calcium stearate, zinc stearate, magnesium stearate, and so forth; hydrocarbon waxes, including paraffin waxes, polyolefin and oxidized polyolefin waxes, and microcrystalline waxes. Particularly suitable lubricants are adds, salts, or amides of stearic acid, such as pentaerythritol tetrastearate, calcium stearate, or N,N′-ethylenebisstearamide. When employed, the lubricant(s) typically constitute from about 0.05 wt. % to about 1.5 wt. %, and in some embodiments, from about 0.1 wt. % to about 0.5 wt. % (by weight) of the polymer composition.
The polymer composition can also include additives that can allow the composition to be used in a particular application and/or processed according to a particular method. For instance, in one embodiment, the polymer composition can include a laser activatable additive and as such the formed polymer composition can be “laser activatable” in the sense that it contains an additive that is activated by a laser direct structuring (“LDS”) process. In such a process, the additive is exposed to a laser that causes the release of metals. The laser thus can be used to draw a pattern of conductive elements onto an article formed of the polymer composition and can leave behind a roughened surface containing embedded metal particles. These particles act as nuclei for the crystal growth during a subsequent plating process (e.g., copper plating, gold plating, nickel plating, silver plating, zinc plating, tin plating, etc).
The laser activatable additive generally includes spinel crystals, which may include two or more metal oxide cluster configurations within a definable crystal formation. For example, the overall crystal formation may have the following general formula:
AB2O4
wherein,
Typically, A in the formula above provides the primary cation component of a first metal oxide cluster and B provides the primary cation component of a second metal oxide cluster. These oxide clusters may have the same or different structures. In one embodiment, for example, the first metal oxide cluster has a tetrahedral structure and the second metal oxide cluster has an octahedral cluster. Regardless, the clusters may together provide a singular identifiable crystal type structure having heightened susceptibility to electromagnetic radiation. Examples of suitable spinel crystals include, for instance, MgAl2O4, ZnAl2O4, FeAl2O4, CuFe2O4, CuCr2O4, MnFe2O4, NiFe2O4, TiFe2O4, FeCr2O4, MgCr2O4, etc. Copper chromium oxide (CuCr2O4) is particularly suitable for use in the present invention and is available from Shepherd Color Co. under the designation “Shepherd Black 1G.”
When included, a laser activatable additive typically constitutes from about 0.1 wt. % to about 30 wt. %, in some embodiments from about 0.5 wt. % to about 20 wt. %, and in some embodiments, from about 1 wt. % to about 10 wt. % of the polymer composition.
The liquid crystalline polymer, fibers, and other optional additives may be melt blended together within a temperature range of from about 200° C. to about 450° C., in some embodiments, from about 220° C. to about 400° C., and in some embodiments, from about 250° C. to about 350° C. to form the polymer composition. Any of a variety of melt blending techniques may generally be employed. For example, the materials (e.g., liquid crystalline polymer, fibers, etc.) may be supplied separately or in combination to an extruder that includes at least one screw rotatably mounted and received within a barrel (e.g., cylindrical barrel) and may define a feed section and a melting section located downstream from the feed section along the length of the screw.
The extruder may be a single screw or twin screw extruder. Referring to
A feed section 132 and melt section 134 are defined along the length of the screw 120. The feed section 132 is the input portion of the barrel 114 where the liquid crystalline polymer is added. The melt section 134 is the phase change section in which the liquid crystalline polymer is changed from a solid to a liquid. While there is no precisely defined delineation of these sections when the extruder is manufactured, it is well within the ordinary skill of those in this art to reliably identify the feed section 132 and the melt section 134 in which phase change from solid to liquid is occurring. Although not necessarily required, the extruder 80 may also have a mixing section 136 that is located adjacent to the output end of the barrel 114 and downstream from the melting section 134. If desired, one or more distributive and/or dispersive mixing elements may be employed within the mixing and/or melting sections of the extruder. Suitable distributive mixers for single screw extruders may include, for instance, Saxon, Dulmage, Cavity Transfer mixers, etc. Likewise, suitable dispersive mixers may include Blister ring, Leroy/Maddock, CRD mixers, etc. As is well known in the art, the mixing may be further improved by using pins in the barrel that create a folding and reorientation of the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers, and Vortex Intermeshing Pin mixers.
The fibers of the polymer composition may generally be added at any location of the extruder, such as to the hopper 40 or at a location downstream therefrom. In one particular embodiment, the fibers are added a location downstream from the point at which the liquid crystalline polymer is supplied, but yet prior to the melting section. In
Regardless of the manner in which it is formed, the melt viscosity of the resulting polymer composition is generally low enough so that it can readily flow into the cavity of a mold to form the walls of a product, e.g., a connector. For example, in one particular embodiment, the polymer composition may have a melt viscosity of from about 0.5 to about 100 Pa-s, in some embodiments from about 1 to about 80 Pa-s, and in some embodiments, from about 5 to about 50 Pa-s, determined at a shear rate of 1000 seconds−1. Melt viscosity may be determined in accordance with ASTM Test No. 1238-70 at a temperature of 350° C.
To help achieve the desired melt viscosity, one or more functional additives may be employed as flow modifiers that interact with the liquid crystalline polymer to reduce its melt viscosity. The functional additives used as flow modifiers may be mono-, di-, trifunctional, etc., and may contain one or more reactive functional groups, such as hydroxyl, carboxyl, carboxylate, ester, and primary or secondary amines. Hydroxy-functional additives are particularly suitable flow modifiers as they contain hydroxyl functional groups that can react with the polymer chain to shorten its length and thus reduce melt viscosity. When employed, such hydroxy-functional flow modifiers typically constitute from about 0.05 wt. % to about 4 wt. % of the polymer composition. One example of such a hydroxyl-functional flow modifier is an aromatic diol, such as hydroquinone, resorcinol, 4,4′-biphenol, etc., as well as combinations thereof. Such aromatic dials may constitute from about 0.01 wt. % to about 1 wt. %, and in some embodiments, from about 0.05 wt. % to about 0.4 wt. % of the polymer composition.
Water is also a suitable hydroxyl-functional flow modifier, and can be used alone or in combination with other hydroxyl-functional flow modifiers. If desired, water can be added in a form that under process conditions generates water. For example, the water can be added as a hydrate that under the process conditions (e.g., high temperature) effectively “loses” water. Such hydrates include alumina trihydrate (ATH), copper sulfate pentahydrate, barium chloride dihydrate, calcium sulfate dihydrate, etc., as well as combinations thereof. When employed, the hydrates may constitute from about 0.02 wt. % to about 2 wt. %, and in some embodiments, from about 0.05 wt. % to about 1 wt. % of the polymer composition.
In addition to those noted above, still other functional additives may be employed as flow modifiers in the polymer composition. For instance, aromatic dicarboxylic acids can be employed that generally act to combine smaller chains of the polymer together after they have been cut by other types of functional compounds. This maintains the mechanical properties of the composition even after its melt viscosity has been reduced. Suitable aromatic dicarboxylic acids for this purpose may include, for instance, terephthalic acid, 2,6-napthalenedicarboxylic acid, isophthalic acid, 4,4′-bibenzoic acid, 2-methylterephthalic acid, etc., as well as combinations thereof. When employed, such dicarboxylic acids typically constitute from about 0.001 wt. % to about 0.5 wt. %, and in some embodiments, from about 0.005 wt. % to about 0.1 wt. % of the polymer composition.
In one embodiment, the polymer composition can employ a mixture of functional additives as flow modifier. For instance the mixture can contain a combination of an aromatic diol, hydrate, and aromatic dicarboxylic acid. A flow modifier that is a combination of functional additives can reduce melt viscosity and improve flow, but without having an adverse impact on mechanical properties. For instance, aromatic dials can constitute from about 15 wt. % to about 45 wt. % of the flow modifier mixture, hydrates can constitute from about 45 wt. % to about 75 wt. % of the flow modifier mixture, and aromatic dicarboxylic acids can constitute from about 1 wt. % to about 15 wt. % of flow modifier mixture. The flow modifier mixture can be included in the polymer composition in an amount similar to that of a single flow modifier, e.g., from about 0.001 wt. % to about 2 wt. %, from about 0.01 wt. % to about 1 wt. %, or from about 0.02 wt % to about 0.5 wt. % of the polymer composition.
Conventionally, it was believed that polymer compositions having low viscosity would not also possess sufficiently good thermal and mechanical properties to enable their use in certain types of applications. Contrary to conventional thought, however, the polymer composition having a low viscosity has been found to possess excellent mechanical properties. The composition may, for instance, possess good tensile and flexural mechanical properties. For example, the polymer composition may exhibit a flexural modulus of from about 10,000 MPa to about 30,000 MPa, in some embodiments from about 12,000 MPa to about 28,000 MPa, and in some embodiments, from about 16,000 MPa to about 25,000 MPa; a flexural strength of from about 100 to about 500 MPa, in some embodiments from about 150 to about 350 MPa, and in some embodiments, from about 175 to about 300 MPa; and/or a flexural break strain of about 0.5% or more, in some embodiments from about 0.6% to about 10%, and in some embodiments, from about 0.8% to about 3.5%. The flexural properties may be determined in accordance with ISO Test No. 178 (technically equivalent to ASTM D790) at 23° C.
The polymer composition may also exhibit a tensile strength of from about 50 to about 500 MPa, in some embodiments from about 100 to about 400 MPa, and in some embodiments, from about 125 to about 350 MPa; a tensile break strain of about 0.5% or more, in some embodiments from about 0.6% to about 10%, and in some embodiments, from about 0.8% to about 3.5%; and/or a tensile modulus of from about 10,000 MPa to about 30,000 MPa, in some embodiments from about 12,000 MPa to about 28,000 MPa, and in some embodiments, from about 15,000 MPa to about 25,000 MPa. The tensile properties may be determined in accordance with ISO Test No. 527 (technically equivalent to ASTM D638) at 23° C.
Charpy notched impact strength is greater than about 10 kJ/m2, in some embodiments from about 5 to about 40 kJ/m2, and in some embodiments, from about 6 to about 30 kJ/m2, measured at 23° C. according to ISO Test No. 179-1 (technically equivalent to ASTM D256, Method B).
The deflection temperature under load (“DTUL”), a measure of short term heat resistance, may, for instance, range from about 200° C. to about 300° C., in some embodiments from about 210° C. to about 280° C., and in some embodiments, from about 215° C. to about 260° C. Such high DTUL values can, among other things, allow the use of high speed processes often employed during the manufacture of electrical components such as connectors.
The polymer composition may be molded into a desired article using techniques as are known in the art. In one embodiment, a shaped article can be molded using an injection molding process in which dried and preheated plastic granules are injected into the mold. The resulting formed article may have any of a variety of different configurations.
Formation techniques are in no way limited to injection molding processes, however, and other formation processes, such as other melt processing formation processes, can be utilized. Suitable melt extrusion techniques may include, for instance, tubular trapped bubble film processes, flat or tube cast film processes, slit die flat cast film processes, etc. The resulting shaped article may have a variety of different forms, such as sheets, films, tubes, etc.
In one embodiment, the polymer composition can be shaped to form an article that is thin in nature and can, for instance, have a thickness of about 10 millimeters or less, in some embodiments from about 0.01 to about 8 millimeters, in some embodiments from about 0.05 to about 6 millimeters, and in some embodiments, from about 0.1 to about 2 millimeters.
Metallized conductive elements may be formed on a shaped article using a laser direct structuring process (“LDS”). Activation with a laser causes a physio-chemical reaction in which spinel crystals included as an additive in the polymer composition are cracked open to release metal atoms. These metal atoms can act as a nuclei for metallization (e.g., reductive copper coating). The laser also creates a microscopically irregular surface and ablates the polymer matrix, creating numerous microscopic pits and undercuts in which the metal can be anchored during metallization.
In one embodiment, the polymer composition can be utilized in forming an article that has previously required the utilization of a metal structural material for strength. For instance, the polymeric composition can be utilized in formation of metallized components for automobiles, trucks, commercial airplanes, aerospace, rail, household appliances, computer hardware, hand held devices, recreation and sports, structural component for machines, structural components for buildings, etc. Suitable electronic device may include, for instance, wireless devices, capacitors (e.g., as a cap for the capacitor), electrical connectors, processors, etc.
Wireless electronic devices are particularly suitable for incorporation of articles formed of the polymer composition. For example, a molded article formed by the polymer composition may serve as a housing for a wireless electronic device. In such embodiments, a component of the wireless electronic device such as the antenna may be disposed on and/or within the polymer composition during the molding process. Other discrete components can also be embedded within the polymer composition, such as metal stampings, bushings, electromechanical parts, filtration materials, metal reinforcement and other discrete parts that are combined into a single unitary device through the injection of the polymer composition around the carefully placed parts.
Examples of suitable wireless electronic devices may include a desktop computer or other computer equipment, a portable electronic device, such as a laptop computer or small portable computer of the type that is sometimes referred to as “ultraportables.” In one suitable arrangement, the portable electronic device may be a handheld electronic device. Examples of portable and handheld electronic devices may include cellular telephones, media players with wireless communications capabilities, handheld computers (also sometimes called personal digital assistants), remote controls, global positioning system (“GPS”) devices, and handheld gaming devices. The device may also be a hybrid device that combines the functionality of multiple conventional devices. Examples of hybrid devices include a cellular telephone that includes media player functionality, a gaming device that includes a wireless communications capability, a cellular telephone that includes game and email functions, and a handheld device that receives email, supports mobile telephone calls, has music player functionality and supports web browsing.
Referring to
The polymer composition may be employed to form any portion of the electronic device 100. In most embodiments, however, the polymer composition is employed to form all or a portion of the housing 86 and/or 88. For example, the housing 86 shown in
Although not expressly shown, the device 100 may also contain circuitry as is known in the art, such as storage, processing circuitry, and input-output components. Wireless transceiver circuitry may be used to transmit and receive radio-frequency (RF) signals. Communications paths such as coaxial communications paths and microstrip communications paths may be used to convey radio-frequency signals between transceiver circuitry and antenna structures. A communications path may be used to convey signals between the antenna structure and circuitry. The communications path may be, for example, a coaxial cable that is connected between an RF transceiver (sometimes called a radio) and a multiband antenna.
Another example of an electronic device that may be formed form the polymer composition is a connector, a representative example of which is shown in
The interior walls of the first housing 10 and/or second housing 20 may have a relatively small width dimension, and can be formed from the polymer composition of the present invention. The walls are, for example, shown in more detail in
In addition to or in lieu of the walls, it should also be understood that any other portion of the connector may also be formed from the polymer composition. For example, the connector may also include a shield that encloses the housing. Some or all of the shield may be formed from the polymer composition of the present invention. For example, the housing and the shield can each be a one-piece structure unitarily molded from the polymer composition. Likewise, the shield can be a two-piece structure that includes a first shell and a second shell, each of which may be formed from the polymer composition of the present invention.
The present invention may be better understood with reference to the following examples.
Injection Molding: Tensile bars are injection molded to ISO 527-1 specifications according to standard ISO conditions. Temperatures are 313° C., 316° C., 321° C. and 317° C. (rear to nozzle) with a mold temperature of 135° C. and an injection speed of 275 mm/s.
Melt Viscosity: The melt viscosity (Pa-s) was determined in accordance with ISO Test No. 11443 at 350° C. and at a shear rate of 400 s−1 and 1000 s−1 using a Dynisco 7001 capillary rheometer. The rheometer orifice (die) had a diameter of 1 mm, length of 20 mm, L/D ratio of 20.1, and an entrance angle of 180°. The diameter of the barrel was 9.55 mm±0.005 mm and the length of the rod was 233.4 mm.
Deflection Temperature Under Load (“DTUL”): The deflection under load temperature was determined in accordance with ISO Test No. 75-2 (technically equivalent to ASTM D648-07). More particularly, a test strip sample having a length of 80 mm, thickness of 10 mm, and width of 4 mm was subjected to an edgewise three-point bending test in which the specified load (maximum outer fibers stress) was 1.8 megaPascals. The specimen was lowered into a silicone oil bath where the temperature is raised at 2° C. per minute until it deflects 0.25 mm (0.32 mm for ISO Test No. 75-2).
Tensile Properties: Tensile properties are tested according to ISO Test No. 527 (technically equivalent to ASTM D638). Modulus and strength measurements are made on the same test strip sample having a length of 80 mm, thickness of 10 mm, and width of 4 mm. The testing temperature is 23° C., and the testing speeds are 1 or 5 mm/min.
Flexural Properties: Flexural properties are tested according to ISO Test No. 178 (technically equivalent to ASTM D790). This test is performed on a 64 mm support span. Tests are run on the center portions of uncut ISO 3167 multi-purpose bars. The testing temperature is 23° C. and the testing speed is 2 mm/min.
Notched Charpy Impact Strength: Notched Charpy properties are tested according to ISO Test No. ISO 179-1 (technically equivalent to ASTM D256, Method B). This test is run using a Type A notch (0.25 mm base radius) and Type 1 specimen size (length of 80 mm, width of 10 mm, and thickness of 4 mm). Specimens are cut from the center of a multi-purpose bar using a single tooth milling machine. The testing temperature is 23° C.
Unnotched Charpy Impact Strength: Unnotched Charpy properties were tested according to ISO Test No. 180 at 23° C. (technically equivalent to ASTM D256). The test is run using a Type 1 specimen (length of 80 mm, width of 10 mm and thickness of 4 mm). Specimens are cut from the center of a multi-purpose bar using a single tooth milling machine. The testing temperature is 23° C.
Density: Density was determined according to ISO Test No. 1183 (technically equivalent to ASTM D792). The specimen was weighed in air then weighed when immersed in distilled water at 23° C. using a sinker and wire to hold the specimen completely submerged as required.
Blister Free Temperature: To test blister resistance, a 127×12.7×0.8 mm test bar is molded at 5° C. to 10° C. higher than the melting temperature of the polymer resin, as determined by DSC. Ten (10) bars are immersed in a silicone oil at a given temperature for 3 minutes, subsequently removed, cooled to ambient conditions, and then inspected for blisters (i.e., surface deformations) that may have formed. The test temperature of the silicone oil begins at 250° C. and is increased at 10° C. increments until a blister is observed on one or more of the test bars. The “blister free temperature” for a tested material is defined as the highest temperature at which all ten (10) bars tested exhibit no blisters. A higher blister free temperature suggests a higher degree of heat resistance.
Warpage-LGA: The warpage is determined by first forming an injection molded line grid array (“LGA”) connector (size of 49 mm×39 mm×1 mm) from a polymer composition sample. A Cores' coplanarity measuring module, model core9037a, is used to measure the degree of warpage of the molded part. The test is performed; connector as molded (unaged), and conditioned in 20 minute temperature cycle that ramps from ambient temperature to 270° C., is maintained for 3 minutes and ramped back to room temperature (aged).
A 2 liter flask was charged with HBA (538.7 g), TA (162 g), BP (145.2 g), IA (54 g), HQ (57.3 g) and 50 mg of potassium acetate. The flask next was equipped with C-shaped stirrer, a thermocouple, a gas inlet, and distillation head. The flask was placed under a low nitrogen purge and acetic anhydride (99.7% assay, 686 g) was added. The milky-white slurry was agitated at 75 rpm and heated to 140° C. over the course of 95 minutes using a fluidized sand bath. After this time, the mixture was then gradually heated to 360° C. steadily over 300 minutes. Reflux was seen once the reaction exceeded 140° C. and the overhead temperature increased to approximately 115° C. as acetic acid byproduct was removed from the system. During the heating, the mixture grew yellow and slightly more viscous and the vapor temperature gradually dropped to 90° C. Once the mixture had reached 360° C., the nitrogen flow was stopped. The flask was evacuated below 20 psi and the agitation slowed to 30 rpm over the course of 45 minutes. As the time under vacuum progressed, the mixture grew viscous. After 63 minutes, in the final vacuum step, torque (20 in/oz) was recorded as seen by the strain on the agitator motor. The reaction was then stopped by releasing the vacuum and stopping the heat flow to the reactor. The flask was cooled and then polymer was recovered as a solid, dense yellow-brown plug. Sample for analytical testing was obtained by mechanical size reduction.
Thermal Behavior (DSC Second Cycle)
Tm=326.5° C.
Tc=285.5° C.
Melt Viscosity (Scanning Shear, 350° C.)
MV (1000 s−1)=85 Pa-s
MV (400 s−1)=137 Pa-s
A 2 liter flask was charged with HBA (547 g), TA (139.8 g), BP (150.6 g), IA (79.5 g), HQ (56.3 g) and 20 mg of potassium acetate. The flask next was equipped with C-shaped stirrer, a thermocouple, a gas inlet, and distillation head. The flask was placed under a low nitrogen purge and acetic anhydride (99.7% assay, 692.7 g) was added. The milky-white slurry was agitated at 75 rpm and heated to 140° C. over the course of 95 minutes using a fluidized sand bath. After this time, the mixture was then gradually heated to 350° C. steadily over 300 minutes. Reflux was seen once the reaction exceeded 140° C. and the overhead temperature increased to approximately 115° C. as acetic acid byproduct was removed from the system. During the heating, the mixture grew yellow and slightly more viscous and the vapor temperature gradually dropped to 90° C. Once the mixture had reached 350° C., the nitrogen flow was stopped. The flask was evacuated below 20 psi and the agitation slowed to 30 rpm over the course of 45 minutes. As the time under vacuum progressed, the mixture grew viscous. After 33 minutes, in the final vacuum step, torque (20 in/oz) was recorded as seen by the strain on the agitator motor, The reaction was then stopped by releasing the vacuum and stopping the heat flow to the reactor. The flask was cooled and then polymer was recovered as a solid, dense yellow-brown plug. Sample for analytical testing was obtained by mechanical size reduction.
Compositions were formed with liquid crystalline polymers as described herein. The non-HNA liquid crystal polymer (LCP) formulation may be formed as described in Example 1 or Example 2, above. The LCP including HND can be formed according to standard technologies such as described herein. Formulation materials included cut glass fibers (13 micron, 4 mm cut length OCV® available from Owens Corning) and a lubricant (commercial grade pentaerythritol tetrastearate Glycolube® P available from Lonza, Inc. of Allendale, N.J.). To form the compositions, the polymers were dried for 4 hours following formation at 275° C. prior to compounding. All raw materials were added to a co-rotating, twin screw extruder (70 mm diameter, 32 LAD) with the glass fiber addition point being downstream of the resin addition point. Process conditions were set for each system based on the polymer melt point, viscosity, etc. Compounded material was stranded using a water bath and pelletized. Resultant pellets were dried overnight at 130° C. and injection molded as described for testing.
Formulations of each sample are described in Table 1, below. Values are provided as weight percentage.
TABLE 1
Sample 1
Sample 2
LCP including HNA
64.7
—
LCP - non-HNA
—
64.7
Glass fiber
35
35
Lubricant
0.3
0.3
Total
100
100
The testing results for the samples are provided in Table 2, below. It is clear that by utilization of the resin with no naphthenic acid derivatives there is a 23.8% improvement in tensile modulus and a 19% improvement in flexural modulus.
TABLE 2
Sample 1
Sample 2
Density (kg/m3)
1670
1670
Tensile Modulus (1 mm/s; MPa)
16000
21000
Tensile Strength (5 mm/s; MPa)
150
155
Flexural Modulus (23° C.; MPa)
17000
21000
Flexural Strength (23° C.; MPa)
225
225
Flexural strain at break (%)
2.1
1.7
Liquid crystalline polymers and compositions were formed with the compositions including an increased amount of glass fibers. The non-HNA liquid crystal polymer (LCP) formulation may be formed as described in Example 1 or Example 2, above. Formulations and testing results are provided in Table 3, below. As can be seen, with increase of the glass fiber loading, there was an approximately 19.9 MPa increase in tensile modulus and about 17.4 increase in flexural modulus for the naphthenic acid-free liquid crystalline polymer as compared to the comparative polymer. This further supports the understanding that the increase in modulus is due to the lack of naphthenic acid in the liquid crystalline polymer.
TABLE 3
Sample 3
Sample 4
LCP including HNA
49.7
—
LCP - non-HNA
—
49.7
Glass fiber
50.0
50.0
Lubricant
0.3
0.3
Total
100.0
100.0
Melt Viscosity (1,000 sec−1 at
52.9
60.0
350° C.; Pa-s)
Melt Viscosity (400 sec−1 at
79.6
89.4
350° C.; Pa-s)
Tensile Modulus (1 mm/s; MPa)
20111 ± 535
24122 ± 153
Tensile Strength (5 mm/s; MPa)
122.5 ± 8.4
133.7 ± 7.0
Tensile Strain at break (%)
0.9 ± 0.2
0.7 ± 0.1
DTUL (° C.)
263.9 ± 1.1
253.9 ± 0.3
Flexural Modulus (23° C.; MPa)
20714 ± 350.7
24327 ± 232.8
Flexural Strength (23° C.)
195.3 ± 8.7
193.2 ± 4.4
Flexural strain at break (%)
1.5 ± 0.1
1.1 ± 0.0
Charpy Unnotched Impact Strength
23.1 ± 3.5
19.4 ± 2.8
(kJ/m2)
Charpy Notched Impact Strength
14.5 ± 1.3
12.7 ± 2.2
(kJ/m2)
Compositions were formed using milled glass fibers as additive with liquid crystal polymers. The non-HNA liquid crystal polymer (LOP) formulation may be formed as described in Example 1 or Example 2, above. Glass fiber additives were as follows:
To form the composition, the polymers were dried overnight at 275° following formation prior to compounding. All raw materials were added to a co-rotating, twin screw extruder (25 mm diameter or 32 mm diameter) with the milled glass fiber addition point being downstream of the resin addition point. Process conditions were set for each system based on polymer melt point, viscosity, etc. Compounded material was stranded using a water bath and pelletized. Resultant pellets were dried overnight at 130° C. and injection molded as described above. Formulations and testing results are presented in Table 4, below.
TABLE 4
Sample 5
Sample 6
Sample 7
LCP including HNA
69.7
69.7
LCP - non-HNA
—
—
69.7
Glass fibers (1)
30
—
—
Glass fibers (2)
30
30
Lubricant
0.3
0.3
0.3
Total
100
100
100
Blister Free Temperature (° C.)
270
260
290
Melt Viscosity (1,000 sec−1 at 350° C.; Pa-s)
22.2
21.7
24.3
Melt Viscosity (400 sec−1 at 350° C.; Pa-s)
29
28.4
30.2
Tensile Modulus (1 mm/s; MPa)
12255 ± 79.0
11111 ± 72.1
16244 ± 106.7
Tensile Strength (5 mm/s; MPa)
160 ± 12.1
158 ± 1.4
168 ± 2.5
Tensile Strain at break (%)
3.13 ± 0.47
3.69 ± 0.08
1.94 ± 0.04
DTUL (° C.)
239.0 ± 1.1
240.1 ± 1.7
226.7 ± 0.6
Flexural Modulus (23° C.; MPa)
12993 ± 101
12184 ± 72
16605 ± 40
Flexural Strength (23° C.; MPa)
*
*
178 ± 1.0
Flexural strain at break (%)
*
*
2.7 ± 0.040
Charpy Notched Impact Strength (kJ/m2)
62.4 ± 7.6
58.5 ± 9.7
27.7 ± 3.9
LGA Peak Mesh Load (lbf)
9.3 ± 0.13
9.1 ± 0.59
8.6 ± 0.36
LGA Warpage (as molded) (mm)
1.010 ± 0.06
1.055 ± 0.11
0.843 ± 0.12
LGA Warpage (post reflow) (mm)
3.038 ± 0.152
3.185 ± 0.287
3.072 ± 0.224
Peak Injection Pressure - LGA (psi)
5388
5457
4983
Flatness as molded (mm)
0.0027
—
0.0018
Flatness post-simulated (mm)
0.0018
—
0.0015
* Indicates that the sample did not break during the flexural bend. It reached 3.5% strain without indicating failure.
As can be seen the utilization of the milled glass fibers with the non-HNA liquid crystalline polymers provided for a significant increase in tensile and flexural modulus relative to the comparison sample.
Materials and methods as described were utilized to form liquid crystalline polymer compositions. The compositions were then used to form injection molded testing bars as described above. Formulations and testing results are summarized in Table 5, below.
TABLE 5
Sample 8
Sample 9
Sample 10
LCP including HNA
59.7
59.7
LCP - non-HNA
—
—
59.7
Glass fibers (1)
40
—
—
Glass fibers (2)
40
40
Lubricant
0.3
0.3
0.3
Total
100
100
100
Melt Viscosity (1,000 sec−1 350° C.; Pa-s)
49.4
45.3
39.6
Melt Viscosity (400 sec−1 at 350° C.; Pa-s)
72.7
63.9
54.3
Tensile Modulus (1 mm/s; MPa)
13767 ± 59.0
11293 ± 65.4
18745 ± 96.8
Tensile Stress (5 mm/s; MPa)
147 ± 4.1
131 ± 4.0
153 ± 3.2
Tensile Strength (%)
2.852 ± 0.2
2.98 ± 1.0
1.438 ± 0.1
DTUL (° C.)
254 ± 2.1
241 ± 3.0
242 ± 1.1
Flexural Modulus (23° C.; MPa)
14911 ± 292.0
12742 ± 61.7
19395 ± 87.0
Flexural Strength (23° C.) (MPa)
181 ± 2.3
156 ± 1.0
190 ± 2.6
Flexural strain at break (%)
2.80 ± 0.10
3.33 ± 0.10
1.88 ± 0.08
Charpy Notched Impact Strength (kJ/m2)
39.1 ± 5.0
33.2 ± 4.2
18.4 ± 1.5
As can be seen the utilization of the milled glass fibers with the non-HNA liquid crystalline polymers provided for a significant increase in tensile and flexural modulus relative to the comparison sample.
These and other modifications and variations of the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.
Zhao, Xinyu, Gray, Steven, Kim, Young Shin, Nair, Kamlesh, Yung, Paul, Barber, Grant, Maliqi, Ardian
Patent | Priority | Assignee | Title |
11499009, | Nov 21 2018 | Samsung Electronics Co., Ltd. | Liquid crystal polymer, composite composition, article, battery case, and battery |
11661521, | Dec 17 2019 | Ticona LLC | Three-dimensional printing system employing a thermotropic liquid crystalline polymer |
Patent | Priority | Assignee | Title |
4002600, | Mar 27 1973 | Ciba-Geigy Corporation | Linear copolyesters based on terephthalic acid and/or isophthalic acid, a process for their manufacture and their use |
4038416, | Sep 11 1975 | Chugai Seiyaku Kabushiki Kaisha | Pharmaceutical composition and method of the use thereof |
4083829, | May 13 1976 | Celanese Corporation | Melt processable thermotropic wholly aromatic polyester |
4132840, | Jul 10 1975 | Bayer Aktiengesellschaft | Process for coloring polyurethane foams |
4161470, | Oct 20 1977 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid and para-hydroxy benzoic acid capable of readily undergoing melt processing |
4163099, | Sep 27 1977 | DU PONT DE NEMOURS DEUTSCHLAND | Polyesters prepared from NH containing carboxylic acids |
4184996, | Sep 12 1977 | Celanese Corporation | Melt processable thermotropic wholly aromatic polyester |
4219461, | Oct 20 1977 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid, para-hydroxy benzoic acid, aromatic diol, and aromatic diacid capable of readily undergoing melt processing |
4256624, | Jul 02 1979 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid, aromatic diol, and aromatic diacid capable of undergoing melt processing |
4279803, | Mar 10 1980 | Celanese Corporation | Polyester of phenyl-4-hydroxybenzoic acid and 4-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid capable of forming an anisotropic melt |
4318841, | Oct 06 1980 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid, para-hydroxy benzoic acid, terephthalic acid, and resorcinol capable of readily undergoing melt processing to form shaped articles having increased impact strength |
4330457, | Dec 09 1980 | Celanese Corporation | Poly(ester-amide) capable of forming an anisotropic melt phase derived from 6-hydroxy-2-naphthoic acid, dicarboxylic acid, and aromatic monomer capable of forming an amide linkage |
4330668, | May 16 1980 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing aromatic polyester with transition metal salt of naphthenic acid |
4337190, | Jul 15 1980 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid and meta-hydroxy benzoic acid capable of readily undergoing melt processing |
4339375, | Jun 04 1981 | Celanese Corporation | Poly(ester-amide) capable of forming an anisotropic melt phase derived from p-hydroxybenzoic acid, 2,6-dihydroxynaphthalene, carbocyclic dicarboxylic acid, aromatic monomer capable of forming an amide linkage, and, optionally, additional aromatic diol |
4351917, | Apr 06 1981 | Celanese Corporation | Poly(ester-amide) capable of forming an anisotropic melt phase derived from 6-hydroxy-2-naphthoic acid, aromatic monomer capable of forming an amide linkage, and other aromatic hydroxyacid |
4351918, | Apr 06 1981 | Celanese Corporation | Poly(ester-amide) capable of forming an anisotropic melt phase derived from 6-hydroxy-2-naphthoic acid, other aromatic hydroxyacid, carbocyclic dicarboxylic acid, and aromatic monomer capable of forming an amide linkage |
4355132, | Apr 07 1981 | Celanese Corporation | Anisotropic melt phase forming poly(ester-amide) derived from p-hydroxybenzoic acid, 2,6-naphthalenedicarboxylic acid, aromatic monomer capable of forming an amide linkage, and, optionally, hydroquinone and additional carbocyclic dicarboxylic acid |
4355134, | Jun 04 1981 | Celanese Corporation | Wholly aromatic polyester capable of forming an anisotropic melt phase at an advantageously reduced temperature |
4375530, | Jul 06 1982 | Celanese Corporation | Polyester of 2,6-naphthalene dicarboxylic acid, 2,6-dihydroxy naphthalene, terephthalic acid, and hydroquinone capable of forming an anisotropic melt |
4387210, | Dec 24 1980 | Mitsui Toatsu Chemical, Inc. | Process for producing aromatic polyester amide |
4393191, | Mar 08 1982 | Celanese Corporation | Preparation of aromatic polyesters by direct self-condensation of aromatic hydroxy acids |
4421908, | Mar 08 1982 | CELANESE CORPORATION, A DE CORP | Preparation of polyesters by direct condensation of hydroxynaphthoic acids, aromatic diacids and aromatic diols |
4429105, | Feb 22 1983 | Celanese Corporation | Process for preparing a polyester of hydroxy naphthoic acid and hydroxy benzoic acid |
4434262, | Sep 01 1982 | Celanese Corporation | Melt processable blend of a low molecular weight liquid crystalline compound and a polyolefin or polyester |
4473682, | Jul 06 1982 | Celanese Corporation | Melt processable polyester capable of forming an anisotropic melt comprising a relatively low concentration of 6-oxy-2-naphthoyl moiety, 4-oxybenzoyl moiety, 4,4'-dioxybiphenyl moiety, and terephthaloyl moiety |
4511709, | Oct 20 1981 | KOREA ADVANCED INSTITUTE OF SCIENCE AND TECHNOLOGY,,; KOLON INDUSTRIES, INC , A CORP OF SOUTH KOREA | Wholly aromatic or aliphatic aromatic block copolyamides and process therefor |
4522974, | Jul 26 1982 | Celanese Corporation | Melt processable polyester capable of forming an anisotropic melt comprising a relatively low concentration of 6-oxy-2-naphthoyl moiety-4-benzoyl moiety, 1,4-dioxyphenylene moiety, isophthaloyl moiety and terephthaloyl moiety |
4563508, | May 18 1984 | SOLVAY ADVANCED POLYMERS, L L C | Injection moldable aromatic polyesters compositions and method of preparation |
4581399, | Sep 30 1982 | Celanese Corporation | Method for the melt processing of thermotropic liquid crystal polymers |
4603190, | Jul 16 1983 | Bayer Aktiengesellschaft | Thermotropic aromatic polyesters having high rigidity and toughness, process for the production thereof and the use thereof for the production of moulded articles, filaments, fibres and films |
4611025, | Apr 04 1985 | ALLIED CORPORATION, A CORP OF NY | Process for the production of thermoplastic compositions containing thermotropic oligomers and compositions produced by such process |
4650836, | Apr 04 1985 | Liquid crystal polymer method and composition | |
4751128, | Aug 28 1986 | BASF Aktiengesellschaft | Fully aromatic thermotropic polyesters |
4778858, | Mar 05 1987 | CORPUS CHRISTI POLYMERS LLC | Preparation of thermoplastic resin composition by solid state polymerization |
4831104, | Feb 25 1985 | TORAY INDUSTRIES, INC , A CORP OF JAPAN | Thermoplastic aromatic polyamideimide copolymer from polyamide diamine |
4851562, | Dec 03 1986 | Akzo N.V. | Aromatic amide groups-containing diamines and polymers in which these diamines are incorporated |
4904752, | Nov 13 1986 | POLYPLASTICS CO , LTD | Liquid crystal copolyester having blocked molecular chain terminal |
4952662, | Feb 12 1988 | Huels Aktiengaellscaft | Molding compounds comprising a thermoplastically processible, aromatic polyamide |
4968737, | Mar 03 1988 | Huels Aktiengesellschaft | Molding compounds comprising a thermoplastically processible aromatic polyamide |
4980444, | Dec 03 1986 | Akzo N.V. | Aromatic amide groups-containing diamines and polymers in which these diamines are incorporated |
4980504, | Aug 01 1988 | AKZO N V , ARNHEM, THE NETHERLANDS A CORP OF NETHERLANDS | Aromatic amide groups-containing diamines and polymers prepared therefrom |
5066767, | Mar 01 1989 | SOLVAY ADVANCED POLYMERS, L L C | Wholly aromatic polyesters comprising isophthalic acid, terephthalic acid, p-hydroxybenzoic acid, hydroquinone and an arylene diol |
5089594, | Oct 11 1988 | BP Corporation North America Inc | Wholly aromatic polyester of isophthalic acid, terephthalic acid, p-hydroxybenzoic acid, hydroquinone and an arylene diol |
5093464, | Dec 01 1988 | Korea Institute of Science and Technology | Wholly aromatic polyamide from N,N'-bis (4-amino phenyl)-isophthalamide |
5102935, | Sep 13 1988 | Bayer Aktiengesellschaft | Free-flowing polyamide molding compounds and blends |
5120820, | Nov 30 1988 | IDEMITSU KOSAN CO ,LTD | Thermoplastic liquid-crystalline, wholly aromatic polyimide ester from carboxy-N-(carboxyphenyl) phthalimide and aralky, hydroquinone |
5147967, | Oct 11 1988 | SOLVAY ADVANCED POLYMERS, L L C | High strength polymer of hydroquinone poly(iso-terephthalate) containing residues of p-hydroxybenzoic acid |
5162489, | Aug 01 1988 | Akzo N.V. | Polyamide from aromatic amide groups-containing diamine |
5171823, | Dec 27 1991 | DEUTSCHE BANK AG, NEW YORK BRANCH, AS COLLATERAL AGENT | Melt processable thermotropic wholly aromatic polyester containing 6-hydroxy-2-naphthoic acid moieties |
5204417, | Oct 11 1988 | SOLVAY ADVANCED POLYMERS, L L C | High strength polymers and blends of hydroquinone poly(iso-terephthalates) containing residues of p-hydroxybenzoic acid |
5204443, | Apr 19 1991 | DEUTSCHE BANK AG, NEW YORK BRANCH, AS COLLATERAL AGENT | Melt processable poly(ester-amide) capable of forming an anisotropic melt containing an aromatic moiety capable of forming an amide linkage |
5216091, | Oct 11 1988 | SOLVAY ADVANCED POLYMERS, L L C | High strength polymers and blends of hydroquinone poly(iso-terephthalates) containing residues of p-hydroxybenzoic acid |
5221730, | Nov 16 1990 | Ticona LLC | Polyesters from terephthalic acid, 2,6-naphthalenedicarboxylic acid and hydroquinone |
5237038, | Nov 16 1990 | Ticona LLC | Polyesters from terephthalic acid, 2,6-naphthalenedicarboxylic acid, hydroquinone and 4,4'-biphenol |
5258470, | Jun 12 1991 | Huls Aktiengesellschaft | Molding compounds based on aromatic polyamides |
5271865, | Feb 13 1990 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid-crystalline mixture of low viscosity |
5278278, | Jul 28 1986 | Toray Industries, Inc. | Aromatic polyesters having good heat resistance |
5296542, | Oct 11 1988 | SOLVAY ADVANCED POLYMERS, L L C | Heat resistant polymers and blends of hydroquinone poly (isoterephthalates) containing residues of p-hydroxybenzoic acid |
5298593, | Jun 25 1991 | Mitsubishi Petrochemical Company, Ltd. | Method of producing thermotropic liquid crystalline polyester |
5324795, | Jan 19 1990 | Unitika Ltd. | Polymer blend composition for melt molding |
5334343, | Mar 18 1991 | ENICHEM S P A | Polyester compositions with a high crystallization rate |
5352746, | May 11 1989 | Sumitomo Chemical Company, Limited | Liquid crystal polyester resin composition improved in fluidity |
5391688, | Jan 22 1993 | NIPPON MITSUBSHI OIL CORPORATION | Liquid crystalline polyesters |
5399656, | Oct 08 1990 | Sumitomo Chemical Company, Limited | Aromatic polyesters and a method for producing the same |
5446124, | Feb 19 1990 | Sumitomo Chemical Company, Limited | Aromatic oligomer and process for preparing the same |
5480907, | May 16 1991 | Takeda Chemical Industries, Ltd. | Aromatic amide compounds and their production and use |
5496893, | Aug 19 1991 | MISSISSIPPI POLYMER TECHNOLOGIES, INC | Macromonomers having reactive side groups |
5500294, | Oct 22 1993 | Tomoegawa Paper Co., Ltd. | Adhesive tape for electronic parts and liquid adhesive |
5510189, | Jan 22 1994 | Tomoegawa Paper Co., Ltd. | Adhesive tape for electronic parts and liquid adhesive |
5534187, | Mar 29 1994 | Chisso Corporation | Liquid crystalline compound and liquid crystal composition |
5541240, | Mar 15 1994 | Hoechst Celanese Corp. | Method for making blends of liquid crystalline and isotropic polymers |
5541267, | Nov 19 1993 | BASF Aktiengesellschaft | Polyamide compositions comprising aliphatic polyamide and an aromatic polyamide oligomer having improved moisture resistance |
5563216, | Jun 19 1991 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition and preparation thereof |
5573752, | Apr 08 1994 | Bracco International B.V. | Aromatic amide compounds and metal chelates thereof |
5609956, | Mar 30 1995 | Tomoegawa Paper Co., Ltd. | Adhesive tape for electronic parts and liquid adhesive |
5614316, | Jun 08 1995 | TOMOEGAWA PAPER CO , LTD | Adhesive tape for electronic parts and liquid adhesive |
5616680, | Oct 04 1994 | DEUTSCHE BANK AG, NEW YORK BRANCH, AS COLLATERAL AGENT | Process for producing liquid crystal polymer |
5663276, | Jun 15 1993 | Nippon Petrochemicals Company, Limited | Wholly aromatic polyester, composition thereof, and molded article made therefrom |
5766507, | Dec 27 1988 | Polyplastics Co., Ltd. | Liquid-crystal resin composition for molding applications having improved fluidity and satisfactory thermal stability |
5767223, | Jul 29 1996 | Nippon Petrochemicals Company, Limited | Wholly-aromatic thermotropic liquid crystal polyester and sealing material for electric and electronic parts |
5779936, | Jan 25 1994 | JNC Corporation | Liquid crystalline compound and liquid crystal composition containing the same |
5976406, | Feb 03 1997 | Sumitomo Chemical Company, Limited | Liquid crystal polyester resin composition |
5997765, | Feb 19 1996 | Sumitomo Chemical Company, Limited | Liquid crystal polyester resin composition |
6046300, | Dec 26 1997 | Toray Industries, Inc. | Liquid-crystalline resin and thermoplastic resin composition |
6114492, | Jan 14 2000 | Ticona LLC | Process for producing liquid crystal polymer |
6140455, | Nov 12 1998 | Sumitomo Chemical Company, Limited | Liquid crystalline polyester resin for extrusion molding |
6177500, | Jul 08 1997 | Sumitomo Cemical Company, Limited | Aromatic polyester composition |
6268419, | Mar 30 1999 | NEC Electronics Corporation | Method of producing thermotropic liquid crystalline copolyester, thermotropic liquid crystalline copolyester composition obtained by the same method, and molding made of the same composition |
6294618, | Apr 09 1998 | Ticona LLC | Low viscosity liquid crystalline polymer compositions |
6294643, | Apr 20 1999 | Sumitomo Chemical Co., Ltd. | Aromatic polyester and molded article using the same |
6296930, | Jun 08 1998 | SUMITOMO CHEMICAL CO , LTD | Aromatic liquid crystalline polyester resin and resin composition thereof |
6296950, | Mar 30 1999 | Nippon Petrochemical Co., LTD | Method of producing thermotropic liquid crystalline copolyester, thermotropic liquid crystalline copolyester composition obtained by the same method, and molding made of the same composition |
6312772, | Oct 20 1997 | CNA HOLDINGS, INC | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-polyester thermoplastic polymer |
6333393, | Aug 06 1999 | Sumitomo Chemical Company, Limited | Aromatic polyester and molded article using the same |
6376076, | Jun 08 1999 | Sumitomo Chemical Company, Limited | Aromatic liquid crystalline polyester resin and resin composition thereof |
6498274, | Sep 23 1997 | AstraZeneca UK Limited | Amide derivatives for the treatment of diseases mediated by cytokines |
6512079, | Aug 29 2000 | Sumitomo Chemical Company, Limited | Liquid crystalline polyester and method for producing the same |
6514611, | Aug 21 2001 | DEUTSCHE BANK AG, NEW YORK BRANCH, AS COLLATERAL AGENT | Anisotropic melt-forming polymers having a high degree of stretchability |
6582625, | Dec 14 2000 | Sumitomo Chemical Company, Limited | Process for producing thermotropic liquid crystalline polymer |
6613847, | Apr 09 1998 | Ticona LLC | Low viscosity liquid crystalline polymer compositions |
6649730, | Sep 27 2001 | Sumitomo Chemical Company, Limited | Aromatic polyester amide |
6656386, | Feb 23 2001 | UENO FINE CHEMICALS INDUSTRY, LTD | Wholly aromatic heat-stable liquid crystalline polyester resin composition with improved melt flowability |
6680002, | Feb 25 2002 | Sumitomo Chemical Company, Limited | Liquid crystalline polyester resin composition for a connector |
6702956, | Jun 28 2001 | Sumitomo Chemical Company, Limited | Liquid crystal polyester resin mixture |
6740728, | May 24 2002 | L AIR LIQUIDE, SOCIETE ANONYME A DIRECTOIRE ET CONSEIL DE SURVEILLANCE POUR L ETUDE ET L EXPLOITATION DES PROCEDES GEORGES CLAUDE | Methods for the preparation of polyesters, poly(ester amide)s and poly(ester imide)s and uses of the materials obtained therefrom |
6755992, | Nov 12 2001 | Sumitomo Chemical Company, Limited | Liquid crystalline polyester and method for producing thereof |
6867280, | Jan 26 2001 | Sumitimo Chemical Company, Limited; Sumitomo Chemical Company, Limited | Process for producing aromatic liquid crystal polyester |
7014921, | Nov 05 2003 | Sumitomo Chemical Company, Limited | Aromatic liquid-crystalline polyester |
7179401, | Jun 15 2001 | UENO FINE CHEMICALS INDUSTRY, LTD | Thermotropic liquid-crystalline polymer |
7238714, | Sep 03 2003 | ASKAT INC | Aryl or heteroaryl amide compounds |
7335318, | Oct 07 2004 | UENO FINE CHEMICALS INDUSTRY, LTD | Method for manufacturing wholly aromatic liquid-crystalline polyester resin |
7343675, | Nov 12 2004 | Harris Corporation | Method of constructing a structural circuit |
7344657, | Sep 30 2004 | Sumitomo Chemical Company, Limited | Aromatic liquid-crystalline polyester composition and film of the same |
7393467, | Jan 31 2005 | UENO FINE CHEMICALS INDUSTRY, LTD | Wholly aromatic liquid-crystalline polyester and method for preparing the same |
7405250, | Aug 31 2005 | SABIC GLOBAL TECHNOLOGIES IP B V | High flow polyester composition, method of manufacture, and uses thereof |
7507784, | Sep 13 2000 | United States of America as represented by the Administrator of the National Aeronautics and Space Administration | Liquid crystalline thermosets from ester, ester-imide, and ester-amide oligomers |
7534914, | May 04 2004 | RAQUALIA PHARMA INC | Substituted methyl aryl or heteroaryl amide compounds |
7550093, | Feb 07 2006 | Sumitomo Chemical Company, Limited | Liquid-crystalline polyester and solution composition comprising the same |
7592413, | Sep 22 2005 | Ticona LLC | Manufacture of aromatic polyester |
7648748, | Oct 13 2005 | Polyplastics Co., Ltd. | Liquid crystalline resin composition for blow molding |
7754717, | Aug 11 2006 | Amgen Inc | Bis-aryl amide compounds and methods of use |
7759344, | Jan 09 2007 | Amgen Inc | Bis-aryl amide derivatives and methods of use |
7790055, | Jul 03 2006 | ENEOS MATERIALS CORPORATION | Wholly aromatic liquid crystal polyester composition and optical pickup lens holder using same |
7790793, | Feb 14 2003 | Ciba Specialty Chemicals Corp | Amide nucleating agent compositions |
7795315, | Jan 29 2008 | Hoffman-La Roche Inc. | N-(2-amino-phenyl)-amide derivatives |
7803307, | Jun 07 2004 | IONIC MATERIALS, INC | Ultra high-temperature plastic package and method of manufacture |
7816014, | Jan 18 2005 | Sumitomo Chemical Company, Limited | Liquid crystalline polyester and film using the same |
7824572, | Jun 27 2007 | Sumitomo Chemical Company, Limited | Liquid crystalline polyester composition |
7825176, | Aug 31 2005 | SABIC GLOBAL TECHNOLOGIES B V | High flow polyester composition |
7914699, | Jun 22 2004 | TORAY INDUSTRIES, INC | Liquid crystal resin, method for making the same, liquid crystal resin composition, and molded article |
8034255, | Jun 08 2009 | E I DU PONT DE NEMOURS AND COMPANY | Liquid crystal compositions |
8084476, | May 04 2004 | Raqualia Pharma Inc. | Substituted methyl aryl or heteroaryl amide compounds |
8084637, | Apr 22 2010 | Xerox Corporation | Amide gellant compounds with aromatic end groups |
8142683, | Mar 28 2008 | ENEOS MATERIALS CORPORATION | Liquid crystal polyester resin composition for camera module |
8309734, | Oct 29 2008 | Hoffmann-La Roche Inc. | Substituted pyridines as GPBAR1 agonists |
8383759, | Mar 29 2011 | Sumitomo Chemical Company, Limited | Method for producing liquid crystal polyester |
8440780, | Dec 27 2010 | Toray Industries, Inc. | Wholly aromatic liquid crystalline polyester and method of producing the same |
8492500, | Jul 29 2011 | Sumitomo Chemical Company, Limited | Method for producing liquid-crystalline polyester |
8501897, | Jul 28 2011 | Sumitomo Chemical Company, Limited | Method for producing liquid-crystalline polyester |
8609802, | Jan 12 2010 | SHENZHEN WOTE ADVANCED MATERIALS CO , LTD | Production method for a wholly aromatic liquid crystalline polyester resin, a wholly aromatic liquid crystalline polyester resin produced by means of the method, and a compound of the wholly aromatic liquid crystalline polyester resin |
8759474, | Mar 29 2011 | Sumitomo Chemical Company, Limited | Method for producing liquid crystal polyester |
8852730, | Aug 29 2011 | Ticona LLC | Melt-extruded substrate for use in thermoformed articles |
8906258, | Aug 29 2011 | Ticona LLC | Heat-resistant liquid crystalline polymer composition having a low melting temperature |
8916673, | Dec 27 2010 | TORAY INDUSTRIES, INC | Process for producing liquid crystalline polyester resin and apparatus for producing liquid crystalline polyester resin |
9012593, | Jul 20 2010 | SHENZHEN WOTE ADVANCED MATERIALS CO , LTD | Method for preparing an aromatic liquid crystal polyester resin and method for preparing a compound of aromatic liquid crystal polyester resin |
20040135118, | |||
20060019110, | |||
20060073306, | |||
20070106035, | |||
20070185118, | |||
20070232594, | |||
20090001317, | |||
20090111950, | |||
20090275697, | |||
20100130743, | |||
20110071304, | |||
20110184188, | |||
20120022202, | |||
20120095183, | |||
20120329975, | |||
20130048908, | |||
20130048909, | |||
20130048910, | |||
20130048911, | |||
20130048914, | |||
20130052447, | |||
20130053531, | |||
20130053532, | |||
20130053533, | |||
20130062558, | |||
20130197165, | |||
20130270481, | |||
20130331540, | |||
20140088287, | |||
20140256903, | |||
20150038631, | |||
JP2003040989, | |||
JP2004018607, | |||
JP2004256656, | |||
JP2004352862, | |||
JP2011178936, | |||
JP5098168, | |||
KR20130012509, | |||
WO2013074467, |
Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
May 28 2014 | NAIR, KAMLESH | Ticona LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 034810 | /0014 | |
May 28 2014 | KIM, YOUNG SHIN | Ticona LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 034810 | /0014 | |
May 30 2014 | BARBER, GRANT | Ticona LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 034810 | /0014 | |
Jun 03 2014 | YUNG, PAUL | Ticona LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 034810 | /0014 | |
Jun 05 2014 | Ticona LLC | (assignment on the face of the patent) | / | |||
Jun 06 2014 | GRAY, STEVEN | Ticona LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 034810 | /0014 | |
Jun 19 2014 | ZHAO, XINYU | Ticona LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 034810 | /0014 | |
Oct 12 2015 | MALIQI, ARDIAN | Ticona LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 036801 | /0604 |
Date | Maintenance Fee Events |
May 22 2019 | M1551: Payment of Maintenance Fee, 4th Year, Large Entity. |
May 23 2023 | M1552: Payment of Maintenance Fee, 8th Year, Large Entity. |
Date | Maintenance Schedule |
Dec 08 2018 | 4 years fee payment window open |
Jun 08 2019 | 6 months grace period start (w surcharge) |
Dec 08 2019 | patent expiry (for year 4) |
Dec 08 2021 | 2 years to revive unintentionally abandoned end. (for year 4) |
Dec 08 2022 | 8 years fee payment window open |
Jun 08 2023 | 6 months grace period start (w surcharge) |
Dec 08 2023 | patent expiry (for year 8) |
Dec 08 2025 | 2 years to revive unintentionally abandoned end. (for year 8) |
Dec 08 2026 | 12 years fee payment window open |
Jun 08 2027 | 6 months grace period start (w surcharge) |
Dec 08 2027 | patent expiry (for year 12) |
Dec 08 2029 | 2 years to revive unintentionally abandoned end. (for year 12) |